JPH0211589B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula [] [In the formula, X is the same or different, an alkyl group,
haloalkyl group, alkoxy group, phenoxy group,
It represents a cyano group or a nitro group, n represents an integer of 0 to 5, and R represents an alkyl group, a cyclopropyl group, or an alkyl group substituted with an alkylsulfenyl group. However, R represents a tertiary butyl group, X represents a halogen atom or a phenyl group, and n
except when represents 1 or 2. ] Among the two geometric isomers of triazole compounds shown in the following, the olefin proton appears on the higher magnetic field side in the NMR spectrum in deuterated chloroform, and the method for producing the same. To give preferable examples of X, n and R in the compound of the present invention [], straight-chain or branched alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, and butoxy groups, halo-substituted alkyl groups such as trifluoromethyl, phenoxy, phenyl, cyano, or It is a nitro group, and n is particularly preferably 0.1 or 2. Preferred are branched alkyl groups, cyclopropyl groups, or alkyl groups substituted with alkylsulfenyl groups (for example, 2-methylsulfenylpropan-2-yl groups). To date, many synthetic organic compounds have been developed that have activity against pests of agricultural and horticultural crops and have greatly contributed to the stable supply of agricultural and horticultural crops as pesticides, but there are still issues that need to be improved. It is also true that there are many. Such problems may be solved, for example, by developing new, more effective drugs, or by reviewing traditional drugs to establish more effective agricultural systems. I can also think of going. Many synthetic organic compounds have the possibility of the existence of isomers such as geometric and optical isomers due to their chemical structures, and even the drugs actually used as agricultural chemicals contain these isomers. There are many examples where it is still used. It is known that many physiologically active substances having isomers exhibit differences in physiological activity between the isomers, not only in agricultural chemicals but also in many other cases. In recent years, the issue of environmental pollution has been much discussed in the field of agriculture and horticulture, but it is possible to reduce environmental pollution by using one of these isomer mixtures that has more effective activity. That is important. Moreover, this is thought to bring about more economical effects both in the manufacturing process of the compound and in the actual use as an agricultural chemical. From this point of view, it is considered that providing an isomer with more effective activity or providing an intermediate therefor by an industrially feasible method will make a sufficient contribution to this field. The present inventors have the following general formula [] [In the formula, R ₁ is

[expression] or

Represents an imidazolyl group or triazolyl group represented by the formula. R ₂ represents a straight chain or branched alkyl group having 1 to 4 carbon atoms. Y represents a straight-chain or branched alkyl group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, an acetoxy group, a trifluoromethyl group, a dimethylamino group, an alkoxy group represented by OR', or a phenoxy group. R' represents an alkyl group having 1 to 4 carbon atoms or a phenyl group that is unsubstituted or substituted with a halogen atom.
n represents an integer from 0 to 3. ] The azole compound represented by (JP-A-53-130661
Publication) and the following general formula [] [In the formula, Z represents an alkyl group, a cyano group, an alkoxy group, a phenoxy group, a halogen atom or a hydrogen atom, and m represents an integer of 1 to 5. R ₁ is

An imidazolyl group represented by [Formula] or

Represents a triazolyl group represented by [Formula]. R ₂ represents a tert-butyl group or a phenyl group that is unsubstituted or optionally substituted with an alkyl group, an alkoxy group, a phenyl group, or a halogen atom. ] The azole compound represented by
It was discovered that the compound (No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, March 2012) has excellent properties as a bactericidal agent. The triazole compound represented by the general formula [] is disclosed in the above-mentioned publication (Japanese Unexamined Patent Publication No. 130661/1983).
As shown in, for example, it can be produced according to the following reaction, [In the formula, X, n and R have the same meanings as described above. ] It is usually obtained as a mixture of geometric isomers represented by the following general formulas [ ] and [ ]. [In the formula, X, n and R have the same meanings as described above. ] The present inventors continued research from the above standpoint, and as a result (1) One of the geometric isomers of the alcohol compound obtained by reducing each of the geometric isomer ketone compounds of the general formulas [] and []. It has excellent properties as an agricultural and horticultural fungicide, such as having extremely high fungicidal activity against a wider range of plant pathogens than the other. (2) By irradiating one of the geometric isomers or a mixture of geometric isomers of the triazole compound represented by the general formula [], virtually quantitatively,
The inventors have discovered that it is possible to produce geometric isomers of ketone compounds that serve as intermediates for producing more active alcohol compounds, leading to the completion of the present invention. In other words, the two geometric isomers of the triazole compound represented by the general formula
For example, one of the geometric isomers of a triazole compound represented by the general formula [] (hereinafter []-
The olefin proton of -E isomer) is
In the NMR spectrum in deuterated chloroform, the other geometric isomer (hereinafter referred to as []-z isomer)
Alcohol compounds obtained by reducing the []-E isomer (hereinafter referred to as alcohol-E isomers) appear on the higher magnetic field side than the olefin proton of
is an alcohol compound obtained by reducing the []-Z isomer (hereinafter referred to as alcohol-Z isomer)
The []-E isomer can be said to be an important intermediate for producing agricultural and horticultural fungicides with superior properties. []-E isomer can also be obtained pure from the isomer mixture obtained according to the above reaction formula by fractional crystallization or column chromatography (see Reference Example 1), but the method of the present invention can be manufactured more efficiently. That is, by exposing the []-Z isomer to light, it was possible to convert it virtually quantitatively into the []-E isomer. []-Z and []
It has been found that any mixture of -E isomers can be converted under similar conditions virtually quantitatively to the []-E isomer, and the present invention provides a method for preparing the []-E isomer. It can be said that this method provides an excellent method. A more specific method for producing the compound of the present invention will be described below. []-Z isomer or []-Z and []
- by placing the mixture of E isomers in a light-inert solvent under light irradiation, such as a UV lamp or a xenon lamp, or, in the laboratory, under a fluorescent lamp or sunlight. []-E isomer can be produced by placing Commonly used solvents include alcohols such as methanol, ethanol, and propanol, ethers such as ether, tetrahydrofuran, and dioxane, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and aliphatic solvents such as hexane, cyclohexane, and petroleum ether. Examples include hydrocarbons, aromatic hydrocarbons such as benzene, toluene, and xylene. The reaction temperature can be carried out at a temperature at which a normal photoisomerization reaction is carried out, but in actual production it is preferably carried out within the range of 0°C to 100°C. It is of course possible to carry out the reaction by adding a sensitizer used in ordinary photoreactions, such as phenyl ketones such as acetophenone and propiophenone, but no particular advantage is found. The compound of the present invention itself has strong bactericidal activity against various agriculturally harmful pathogenic bacteria, and can be used as a useful fungicide (see Reference Example 2), as well as having herbicidal and plant growth regulating effects. The possibility of use in this field is also recognized. Next, the present invention will be explained in more detail by giving examples and reference examples. Reference example 1 1-(4-methylphenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)
-Synthesis of 1-penten-3-one (geometric isomer mixture) α-(1,2,4-triazol-1-yl)
50 g of pinacolon, 41 g of anhydrous potassium carbonate, 200 ml of acetic anhydride, and 39.7 g of 4-chlorobenzaldehyde were mixed and heated at 90° C. for 12 hours with stirring. After cooling the reaction solution, the precipitate was removed by filtration. Mother liquor at 60℃
The mixture was added dropwise to 500 ml of warm water to decompose the acetic anhydride, then potassium carbonate was added little by little to make it alkaline, and the resulting oil was extracted with 500 ml of ethyl acetate.
The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. A drop of the residue was taken and made into an acetone solution, and gas chromatography was performed under the following conditions, and the retention time was 250 seconds.
The peak corresponding to the E isomer was detected at 300 seconds []-
A peak corresponding to the Z isomer was observed. The abundance ratio determined from the area percentage was 1/4. The conditions for gas chromatography are as follows. Equipment: JEOL 20KFID detector Column: 5% XE-60, carrier Chromosolve W,
1m glass column Column temperature: 200℃ Vaporization chamber temperature: 240℃ Carrier gas: Nitrogen gas 1Kg/cm ² The residue was dissolved in 100ml of benzene, passed through a column containing 1.2Kg of silica gel (100-200 mesh), and then Column chromatography was performed using -hexane/acetone (10/1) as a developing solvent. The fractions corresponding to each obtained isomer were recrystallized from carbon tetrachloride to obtain 29 g of pure []-Z isomer.
(yield 35.9%, n ²² _D 1.5607) and []-E isomer
5.5 g (yield 6.8%, melting point 87-88°C) was obtained. By further passing a developing solvent n-hexane/acetone (10/3), 10 g of α-(1,2,4-triazol-1-yl)pinacolon was recovered. Elemental analysis values and characteristic NMR spectra of each isomer are shown. The NMR spectrum uses deuterochloroform as a solvent and the chemical shifts are shown as δ values using tetramethylsilane as an internal standard. 1-(4-methylphenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-
E isomer of 1-penten-3-one: Elemental analysis C(%) H(%) N(%) Calculated value 71.33 7.12 15.60 As (C ₁₆ H ₁₉ N ₃ O) Analytical value 71.71 7.15 15.20 NMR spectrum 8.30 ( 1H, singlet, triazole proton), 8.07 (1H, singlet, triazole proton), 7.15 (1H, singlet, olefin proton) 1-(4-methylphenyl)-4,4-dimethyl-2-(1,2,4- triazol-1-yl)-
-Z isomer of 1-penten-3-one; Elemental analysis C (%) H (%) N (%) Analysis value 71.50 7.09 17.72 NMR spectrum 8.13 (1H, singlet, triazole proton), 7.95 (1H, singlet, triazole proton), 7.56 (1H, singlet, olefin proton) Example 1 1-(4-methylphenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)
Synthesis of []-E isomer of -1-penten-3-one (compound number 5) 1-(4-methylphenyl)- obtained in Reference Example 1
10.0 g of the []-Z isomer of 4,4-dimethyl-2-(1,2,4-triazol-1-yl)-1-penten-3-one was dissolved in 500 ml of acetone,
The isomerization reaction was carried out at 45°C using an internally illuminated ultraviolet irradiation device equipped with a 500W high-pressure mercury lamp. A small amount of the reaction solution was taken as a sample at any time, and the isomerization ratio []-Z isomer/[]-isomer) was monitored by gas chromatography under the same conditions as in Reference Example 1.The following results were obtained. I got it. Time (min) Isomer ratio ([]-Z/[]-E) 0 100/ 0 15 15/85 30 7/93 60 6/94 After 10 hours, the reaction solution was transferred to a 500 ml eggplant flask and added with acetone under reduced pressure. was distilled off to obtain 9.8 g of crystals. This was recrystallized from carbon tetrachloride and 5.3g (53
%) of crystals were obtained. When an acetone solution of this compound with a melting point of 87-88 DEG C. was subjected to gas chromatography under the above conditions, no peak corresponding to the []-Z isomer was observed. Example 2 1-(4-methylphenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)
Synthesis of []-E isomer from a mixture of geometric isomers of -1-penten-3-one []-E/[]- obtained in the reaction of Reference Example 1
10 g of the isomer reaction mixture of Z = 1/4 was irradiated with ultraviolet rays under the same conditions as in Example 1, and examined by gas chromatography after 9 hours []-E/[]
-Z abundance ratio was approximately 16/1. After evaporating the solvent, the resulting crystals were recrystallized from carbon tetrachloride to isolate 5.2 g of the []-E isomer. Hereinafter, the []-E isomer was produced in the same manner and listed in Table 1. For comparison, the []-Z isomer is also described. As is clear from the table, the olefin proton of the []-E isomer is observed on the higher magnetic field side compared to the []-Z isomer.

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[Table] Reference Example 2 Effect of controlling barley powdery mildew by foliage spraying (seedling test) A 150 ml plastic pot was filled with sand-broken soil, and 10 to 15 barley seeds (variety: Goune Shiseki) were sown. This was cultivated for 7 days in an air-conditioned temperature and humidity range of 18 to 23°C to obtain barley seedlings with the first true leaves developed.
A water diluted solution of the test compound in the form of an emulsion was sprayed onto the seedlings at 10 ml per pot. Barley powdery mildew fungus (Erysiphe) appears on young seedlings after air drying the chemical solution.
graminis) was placed in a constant temperature chamber at 23°C and cultured for 10 days under fluorescent lamp illumination, and then the disease state of the first true leaves was observed. The disease severity was calculated by the following method. That is, they were classified into indices as shown in Table 2 according to the degree of appearance of lesions on the investigated leaves.

[Table] Next, the time after onset of illness was calculated using the following formula. After disease onset (%) = Σ (infection index) × (number of leaves) / (number of investigated leaves) × 100 Next, the control value was calculated from the following formula. Control value (%) = 100 - (incidence in compound-treated area) / (incidence in non-treated area) x 100 The results of this test are shown in Table 3, and as is clear from this accumulation, the present invention The compound exhibits excellent barley powdery mildew control efficacy, and its efficacy is comparable to or superior to a comparative compound used for barley powdery mildew control.

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Claims (1)

[Claims] 1. General formula [In the formula, X is the same or different, an alkyl group,
haloalkyl group, alkoxy group, phenoxy group,
It represents a cyano group or a nitro group, n represents an integer of 0 to 5, and R represents an alkyl group, a cyclopropyl group, or an alkyl group substituted with an alkylsulfenyl group. However, R represents a tertiary butyl group, X represents a halogen atom or a phenyl group, and n
except when represents 1 or 2. ] Among the two geometric isomers of triazole compounds represented by , a geometric isomer compound in which the olefin proton appears on the higher magnetic field side in the NMR spectrum in deuterated chloroform. 2 General formula [In the formula, X is the same or different, an alkyl group,
haloalkyl group, alkoxy group, phenoxy group,
It represents a cyano group or a nitro group, n represents an integer of 0 to 5, and R represents an alkyl group, a cyclopropyl group, or an alkyl group substituted with an alkylsulfenyl group. However, R represents a tertiary butyl group, X represents a halogen atom or a phenyl group, and n
except when represents 1 or 2. ] Among the two geometric isomers of the triazole compound represented by , the geometric isomer in which the olefin proton appears on the lower magnetic field side in the NMR spectrum in deuterated chloroform is isomerized by light irradiation. A method for producing a geometric isomer in which the olefin proton of the above triazole compound appears on the higher magnetic field side in the NMR spectrum in deuterated chloroform. 3 General formula [In the formula, X is the same or different, an alkyl group,
haloalkyl group, alkoxy group, phenoxy group,
It represents a cyano group or a nitro group, n represents an integer of 0 to 5, and R represents an alkyl group, a cyclopropyl group, or an alkyl group substituted with an alkylsulfenyl group. However, R represents a tertiary butyl group, X represents a halogen atom or a phenyl group, and n
except when represents 1 or 2. ] A mixture of two geometric isomers of the triazole compound represented by isomerized by light irradiation, wherein the olefin proton of the triazole compound appears on the higher magnetic field side in the NMR spectrum in deuterated chloroform. Method for producing geometric isomers.